Arylamides of hydroxy naphthoic



Patented Sept. 7," 1943 V n 35232832; I ARYLAMIlJES or mitoxy'pg mi w xUACIDS." a

Geoffrey Jones Marriott and I Kenneth Herbert Saunders, Manchester,England, assignorsto Imperial Chemical Industries Limiterha corpoi aration of Great Britain No Drawing. Original application oddamn, 1939,Serial No. 310,440. Divided'ancfthis aplication January 29, 1941; SerialNo. 376,471.

1 In Great Britain January 3,1939

I 15 Claims. elete-#51 65 j The present invention relatesto the manufac;ture of new compounds and their application in. the colouring ofcellulosic material. More;particularly this invention relates tomakingnew: arylamides of 2:3-hydroxynaphthoic acid and to the colouring ofcellulosie material by-causing the said 2g3-hydroxynaphthoic amides tocouple on the fibre with diazotised aromatic amines] 4 It; is an objectof this invention top-reduce. advantageous results in the colouring andprinting of cellulos'ic textile material. A further obs ject is toprovide new'cheinical compoundswhiph are useful in the art of colouringcellulgsic tex tile material. fAnother object is to prov de a} methodfor' preparing such new chem-ical' co npounds. Still; another object toprovide new compositions of matter and to advancethe gart Other objectswill appear hereinafter.

According to the invention amines which ar e 4-amino-2-di(beta-acetoxyethoxy) -anilides of benzoic acid and phenoxyaceticacids, which acids may carry as nuclear substituentspfor example,alkoxyor halogen, are condensed 2 :3-hydroxynaphthoic acid or asreactive.deriva'- tive: thereof, and hydrolysed so as-tov produce thenew corresponding 2 :3 -hydroxynaphthoic'-2!-: 5'

di(beta-hydroxyethoxy)' .-anilides which are reac tive towards diazocompounds. v is 1:1.

Thus there may be employed, in accordance with the invention,Lamina-2:5'-di(beta-acetoxyethoxy) -ani1ides oi benzoic acid,phenoxyacetic acid and the ortho-, metals-and para-' chloro, -bromo,-methoxy and -ethoxy.deriiflatives thereof such. as the.4eamino-2:5dibeta acetoxyethoxy).-.anilides oi benzoic acid, o-chlO 3 robenzoicacid; m-bromobenzoic acid, p-methoxybenzoic acid, phenoxyacetic acid,and o-chlorophenoxyacetic; acid. v V to By a further feature? of theinvention the said 2::3-hydroxynaphthoib anilides Jareapplied'vito'cellulosic fibre and: the'material coloured by the" application theretoof a 'diazo compound; which is: free of; solubilising groups: such? assulphonic acid; or: carboxylicacid'groups; The 'dia-zo com pound mayhe'- applied in stabilisedfform; e. g; in the form of a metallic doublesalt"or' ma a sulphonate with or without other metallic-salts;

For the purpose of providing diazo compoents wa m be mp oy d i n samaath ollwie mie or lil i anil na m -s l tq- 'niline; o nitroaniline, 2:5-dich1or0ani1ine, 4'-ni-* Vtro-2-aminotoluene, 5-nitro 2-am inotoluene,4- nitro -2-aminoanisole, 5-chloro-z 'aminotoluene, a-chloro 2'nitroan-iline, 3-nitro-4-aminotoluene,

5o 4-chloro 2-aminoanisole; alpha-aminoa'nthra=-= quinone,5-nitro-2-aminoanisole, 3-nitr'o-4-ami noanisole,2-ch1oro-4-benzoylamino-5-methoxyaniline, and 4-benzoylamino-2:5-diethoxyaniline; 1 l Inthis way, orange, red, brown and maroonshadesare obtained of surprisingly good light fastness; I iAlso the 2:3-hydroxynaphthoic-2":5"-' di(beta-hydroxyethoxy) -anilides describedabove, whicharejused as coupling components, possess only: small tomedium affinity for the fibre. This is an advantage when they are usedby textile printers since the uncoloured portions of the printed fabriccan be easily washed to give. a clear'white ,Moreover the shadesobtained are c'apabl'eof being discharged to agood clear white, Isardine-2:5-di-(beta acetoxyethoxyl anilides referred to abovefcanbe made byti nteracting 2:-5-di(beta-acetoxyethoxyyv aniline with the-requisite. carboxylicacid halide, and then' nitratingl' and "reducing.2':5'-di(beta-acetoxyethoxy aniline; can be made as described in Britishp pecifi l cation No. 422,447. r TheTinvention is illustrated but notlimited by the followingexamples, in which, the parts are byweight.Example-I -21 parts of 4-benzoylamino-2:5-di(betaacetoxyethoxyl-aniline, which may be made as descr'ibedrbelow, are heatedwith stirring "in 175 9;? parts of tolueneat 60 6., together with 9.5parts of 2:3-hydroxynaphthoic acid; and 2.7 parts of phosphorustrichloride are added drop by drop during one hour. The mixture-is thenboiled. underrefi'ux for 15 hours, poured'into water and the aqueouslayer made alkaline with sodiumicar bonate and the toluene removed bysteam distillae tion. The insoluble material is filtered ofi, washed anddissolved in'a boiling solution of 10 parts of sodium hydroxide in 600parts of water.

Ifhe solutionso obtained is cooled, filtered and the new amide, ofconstitution 2E3-hydroxynaphthoic -2' :5 7 di- (beta-hydroxyethoxy) 4'benzoylaminoqanilide; precipitated by the addisq tion of acid, filteredoii and driedn 4-benzoy1amino -2 51- di (beta-acetoxyethoxy) aniline (M.P. 110 C.) may be made by condensing benzoylchloride with2:5-di(beta-acetoxyethoxy)-aniline in benzene in the presence ofpotassium acetate followed by nitration in glacial acetic acid andreduction of the resulting benzoyl compound.

Example II parts of the 'newamide madeaccording to Example I are madeinto a paste with parts of 50% Turkey red oil, which has beenneutralised with sodium carbonate, and 100 parts of boiling water areadded followed 'byl0'y'parts' of'sodium 1 hydroxide solutionisp. gr.1.31).

in for 20 minutes, removed, squeezedwell' and then introduced intoa'bath containing 2 parts of diazotised p-chloro-o-nitroaniline per 1000parts of solution. The cotton is turned for 20 minutes in the bath,removedgsqueezed, rinsed; 2 well in cold water and boiled for 20 minutesina-r The resulting solution is diluted with 775 parts of cold Water 1and 50 parts of cotton yarn are immersed there-" solution containing 2parts of sodium carbonate and 3 parts of neutral soap flakes per 1000parts ofeolution. Adull reddish-brown shade of good light -fastness isobtained; 1 by v By replacing p-chloro-o-nitroaniline by theunder-mentioned amines, for vexample, the following shades having goodfastness'properties may be obtained? Shade Amine emp o obtainedrn-Chloroanilinej .Q L. Brownish red. 2:5-dicl1loroaniline. r i

Alpha-aminoanthraquin' Brown.

5-chloro-2-nminotoluene Dull red. 5-nitro-2-aminoanisole -Dull maroon.

4 11itro-2-aminoenisole Dull red.

' Orange brown.

4- (phenoxyacetylamino) -2 5-di (.beta-acetoxy -f ethoxy) -aniline (M.P. 109 C.) may be made by condensing phenoxya'cetyl chloride with2:5-di- .(beta-acetoxyethoxy)-ani1ine in benzene in the presence ofsodium acetate followedby nitration in glacial acetic acid and reductionof the resulting phenoxyacetyl compound; I E :cmg zpZe IV 3 parts of thenewamide made according to Example III are made into a paste with 10parts of: 50% Iurkey red oil, which has been neutralisedwithsodiumcarbonate, and 60 parts of boiling water are ,addedffollowed by 6 partsof sodium hydroxidesolution. (sp. gr. 1.31). Boiling is con tinued untilaclear solution is obtained which is then diluted with 920 parts of coldwater. 50 parts of cotton yarn are 'immersed'in thissolution for minutesand treated with a solution containingz parts of diazotisedp-chloro-o-nitroaniline per 1000 parts of solutioniri the manner '4sWhite cotton cloth is padded in a solution'ofl Alpha-aminoanthraquinone5-chl0ro-2-aminotoluene. 5:nitro-2-aminoanisole...4-nitro-2-aminoanisole described in Example II. A dull reddish-brownshade of good light fastness is obtained.

There may be employed in place of p-chlOroo-nitroaniline, for example,the amines which are indicated below together with the shades ob tainedthereby. l I

"Amine employed 7 z ggggg O-Nitroaniline Orange brown. 2: 5-dichloroaniline Brownish red.

Red. Dull red.

Red.

' Example V 2 2.3 I parts of 4.',-:p-anisoylamino2:5-di(beta-'acetoxyethoxy)aniline, which may be made as described below, are heatedwith stirring in 300 parts of toluene at 60 C. together with 9.5 partso:f, 2:3-hydroxynaphthoic acid, and 2.7 parts of phosphorus trichlorideare added drop by drop The mixture is then boiled duringone hour. underreflux for 15 hours, poured into water and the aqueous layer madealkaline *Withsodium carbonate; and the tolueneiren ioved by st eamdistillation. The insoluble" material is filtered o f, washed anddissolved in a boiling solution of 10 parts of sodium hydroxide in- 600:parts o f water. Thesolution so'obtained is coole cl-, filtered and thenew amide o'f constitution 2 53- hydroxynaphthoic 2' 5' di (beta-hydroxyethoxy) 4-p-an isoylamino anilide,,M. P. 230 CZQprecipit'ated bythe addition of acid, ifilt e red on aniline (lVl.P.'127-'-128 C.)*maybe made by condensing p-anisoyl chloride with 2:5-di(beta-facetoxyethoxy)' -aniline in benzeneiin the presence of potassiumacetate, followed by nitration in glacial acetic acid and reduction oftheresultj ing p-anisoyl compound." n H Example 7 VI 15 parts ofithe newamide made according to Example .-V 25 parts of 50% Turkeyre'd oil',which. has been neutralised with sodium carbonate, and! ZOi parts' ofsodium hydroxide solution (sp.'.gr."

1.31) in 940'parts of water. The'cloth is then printed-with a printingpaste containing:

. Parts The zinc chloride double salt of anthra- -quinone-1-diazoniumchloride '2" A'l2% mucilage of wheat starch-tragacanth (611) 60 40%acetic acid 2 Water l 36 The cloth is dried, immersed for half aminutein a solution containing 10 parts ofsodium bisulphite solution (sp. gr.L34) per 1000 parts at 60 0,, rinsed Wellin cold water and boiled for 10minutes in a solution containing 2 parts of sodium; carbonate and3parts3'of neutral soap flakes .per 1000 parts of solution; Thematerialisthen rinsed in cold Water and dried. A reddish-brownprint ofgood fastness propertiesds obtained. Example VII 024. 7 parts of4-m-bromobenzoylamino-2:l'i-dl- (be'ta-acetoxyi ethoxy) -aniline,whichmaybe made Orange brown. H I

as described below, are heated with stirring in 300 parts of toluene at60 0. together with 9.5 parts of 2:3.-hydroxynaphthoic acid, and 2.7parts of phosphorus trichloride are added drop by drop during one hour.The mixture is then boiled under reflux for 15 hours, poured intowaterand 4-m-bromobenzoylamino-2:5-di(beta-acetoxy ethoxy)-aniline (M.P. 103104 C.) may be made by condensing m-bromobenzoyl-chloride with 2:5- di- (beta-acetoxyethoxy) -aniline in benzene in the presenceof'potassium acetate, followed by ni-- tration in glacial acetic acidand reduction of the resulting m-bromo -benzoyl compound.

Example VIII 3 parts of the new amide made according to Example VII aremade into a paste with parts of 50% Turkey red oil, which hasbeenneutralised with sodium carbonate and 60 parts of boiling water areadded followed by 6 parts of sodium hydroxide solution (sp. gr. 1.31).The resulting solution is diluted with 1000 parts of water containing 10parts of sodium chloride and 50 parts of cotton yarn are immersedtherein for i minutes, removed, squeezed well and then introduced intoabath containing 2 parts of diazotised 5-nitro-2-aminoanisole per 1000parts w of solution. The cotton is turned for 20 minutes in the bath,removed, squeezed, rinsed well in cold water and boiled for 20 minutesina solution containing 2 parts of sodium carbonate and 3 parts of neutralsoap flakes per 1000 parts of solution. A bluish-red shade of good lightfast ness is obtained.

When d-ehlormZ-ammoanisole, 4-chloro-2-l nitro-aniline, oralpha-aminoanthraquinoneis used instead of 5-nitro-2-aminoanisole, thefolv lowing shades are obtained:

Amine employed fiis gi i 4-chloro-2-aminoanis0le Dull red.4-chl0ro-2-nitroaniline B r o w n i s h orange. Alpha-aminoanthraquinoneDo.

This is a division of our application Serial Number 310,440, filedDecember 21, 1939.

As manyapparently widely different embodiments of this invention may bemade without.

- departing from the spirit and scope'thereoi, it is to be understoodthat'we do not limit ourselves 5 to the specific" embodiments thereofexcept as defined in theappended claims.

' We claim: I

1. A compound represented by the formula oc mon in which X is one of agroup consisting ofalk- 15 oxy hydrogen, and halogen and n is notgreater than 2. y 2. The compound represented by the formula -OH 0 CHiOH O-HNGNH-O o GHQ-CO oo nion 3. The compound represented, by theformula ONE-O 060 on;

CZHAOH 4. The compound "represented by the formula OH O CZH-iOE Br 5.The process which comprise making a mixture in toluene of2,3-hydroxynaphthoic acid and an amine represented by the formulaooznrooo ona ooznro o 0*(3113 -c O-EN- inyvhiehl i is one of a groupconsisting of hydrogen, alkoxy and halogen and n is an integer until ananilide is formed which is represented by the formula T ozrnon I xGEOFFREY JONES MARRIOTT. KENNETH HERBERT SAUNDERS.

[not greater than 2, and heating the mixture to boiling in the presenceof phosphorus trichloride

